CN1058643C - Catalytic ZSM-5/metal or ceramic compounded material and its preparation - Google Patents
Catalytic ZSM-5/metal or ceramic compounded material and its preparation Download PDFInfo
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Abstract
The present invention relates to a ZSM-5/metal or ceramic catalytic composite material which is compounded from a ZSM-5 molecular sieve and metal or ceramic basic material carrying the molecular sieve, wherein the basic material has predesigned shape and size similar to bulky or regular fillers, static mixers and irregular catalysts. The composite material reserves the characteristics of the ZSM-5 molecular sieve in catalytic performance, and can satisfy requirements for different reactions by modification. The composite material can satisfy requirements for different processes in engineering property by changing the shape and the size of metal base material, the composite material can be used as a catalytic distilling element and an irregular catalyst for catalytic processes with large treating capacity and high speed of mass transfer and heat transfer.
Description
The invention relates to the catalytic composite materials and the preparation thereof that contain zeolite molecular sieve, specifically directly be compound in the catalytic composite materials and the preparation thereof on metal or ceramic base material surface about the ZSM-5 molecular sieve.
The development and application of catalytic distillation new technology is a kind of new trend, and it fills in solid catalyst in the distillation tower by rights, makes catalyzed reaction separate two traditional technological processs with product and also carries out continuously simultaneously in same tower.This suitable catalyst loading pattern, concrete structure formation is arranged, and this structure formation is called catalytic distillation structure, and it should guarantee that catalyzed reaction carries out expeditiously, guarantee carrying out smoothly of fractionation by distillation process again, promptly it should have catalyzer and two kinds of functions of filler.If in fixed bed fills in tower, then cause pressure drop very big traditional small catalyst particles, still-process is successfully carried out.Should prepare a kind of new catalytic composite materials for this reason, make it not only have advantages of high catalytic activity, and enough gas-liquid channels and enough gas-to-liquid contact areas can be provided after in filling in tower, to guarantee that pressure drop is low, mass-transfer efficiency is high.This shows,, just might be applied as catalytic distillation structure if this new catalytic material has the same with filler or similar shape and size.
Catalytic distillation is compared with traditional chemical technique, advantage with many uniquenesses, one of them is exactly by catalyzed reaction and the isolating combination of product, reactant is in time separated apace with product, and product shifted out reaction zone, thereby make reversible reaction and complex reaction also, the transformation efficiency and the selectivity of cascade reaction be improved.If as fixed bed, product can not in time shift out reaction zone, then can not bring into play the superiority of catalytic distillation fully.Therefore the design of catalytic distillation structure should avoid being similar to the conversion zone existence of little fixed bed as much as possible, and the catalyst activity component is distributed on the catalytic distillation structure with higher separating power equably.
Present three common problems of catalytic distillation structure existence (USP 4232177,4443559, and 4215011,5057468,4847430,4624748, EP 428265A1): I) its shape and size differ bigger with filler, and the design and the operation of still-process brought inconvenience; II) existence can not separate product as the reaction zone of fixed bed effectively in tower; III) make and load and unload difficulty.Therefore, catalytic distillation needs a kind of new catalytic composite materials, and the separating power of existing filler has catalytic performance preferably again, and requires active ingredient to be distributed on the matrix material equably.
Development from special-shaped catalyst.Now adopting maximum is pellet type catalyst, as cylindrical, trilobal etc., loads by the fixed bed mode.In order to improve the utilization ratio of catalyzer, can reduce the granularity of catalyzer, but pressure drop is increased.So developed integral catalyzer, as honeycombed catalyst, provide parallel passage to streams, pressure drop is reduced, geometrical surface increases (Chengdu Univ. of Science ﹠ Technology's journal 2,29～34 (1985)).But lacked the transmission of material between the parallel channels, the existence in passage inner laminar flow district makes the even mass-transfer efficiency of material concentration skewness low simultaneously.If can reduce laminar flow zone, strengthen radial diffusion, the product that catalyst surface is generated enters the main body phase apace, and reactant moves on to catalyst surface fast, then will improve catalyzed reaction efficient.Therefore be necessary to change flow state, reinforcing mass transfer and the heat transfer of material by the geometrical shape that changes catalyzer.
The serious technological process of some internal diffusion as hydrocarbon steam conversion, can not make full use of the activity of such catalysts component simultaneously, and the geometrical surface of granules of catalyst is depended in the reinforcement of process at this moment.If adopt the method that reduces granules of catalyst, then cause pressure drop to increase, therefore should under the condition that guarantees the catalyzer physical strength, change the geometrical shape of catalyzer.At present existing wheel shape, inside and outside gear-like, many sieve plates of thin-walled steering wheel etc., but its wall thickness still differs big (3,1～8 pages of chemical fertilizer and catalysis, 1988) with the effecting reaction layer thickness.
The ZSM-5 molecular sieve was succeeded in developing (USP 3,702,886) from 1972 by the Mobil oil company and through updating afterwards, has been obtained using extremely widely in many chemical processes.If the ZSM-5 molecular sieve is prepared into a kind of catalytic composite materials that meets above-mentioned requirements, for example be prepared into a kind of catalytic distillation structure with shape and size of filler, the application of ZSM-5 molecular sieve is brought into play more fully, brought revolutionary breakthrough and beneficial effect might for some traditional chemical process.
CA 1235684 has described a kind of strainer that directly forms one deck zeolite membrane on sintered glass, and the thickness of zeolite membrane is 1～500 μ m.A kind of mould material of being made up of the zeolite membrane on the porous alumina carrier has been described among the JP-A-63291809.EP 180200 has described a kind of mould material that deposits particulate zeolite on porous substrate, ultra-filtration membrane or sintered glass dipping is gone up ultrafine zeolite particulate alkaline solution and prepares.
Described a kind of synthetic film that has zeolite crystal among the EP 0511739A1, its preparation process comprises: (1) preparation aperture is approximately the porous substrate of 0.1～3 μ m, Al wherein
2O
3Content is at least 90%; (2) at least one surface of this its material is immersed in the slurries of being formed by zeolite crystal and its precursor (making) by silicon source such as water glass or water glass; (3) at least once with base material and this slurry water thermal crystallisation.Forming high-density layer in this mould material mesolite crystal duct He on the surface at base material, thus can be used for separating and refining mixture in useful component.
A kind of method for preparing molecular screen membrane from colloidal sol has been described among the WO 93/17781, this method comprises a kind of the water base of zeolite or alcohol radical sol composition of forming of formation, this sol composition is deposited on a kind of porous support, and this porous support and sol composition are exposed in the water vapour atmosphere under temperature is enough to make the condition of sol composition hydrothermal crystallizing and form zeolite membrane.
People such as Bratton in EP 0481660A1, described a kind of on porous substrate load the film of zeolite type material is arranged, base material be shaped as flat plate, tubular or coiled, porous substrate can be that porous metal, pottery, sintering metal, glass, mineral substance, charcoal or polymkeric substance, porous metal wherein can be that fiber screen shape, Fiber metal combine or sintered metal fiber with sintered metal particle, and typical metal comprises stainless steel, Inconel(nickel alloys), hastelloy, chromium, iron etc.Wherein available porous ceramics, glass, charcoal or mineral intermediate comprise poroid charcoal, silicon carbide, adobe or other silicate minerals.The preparation method of this film be with porous substrate (aperture can be 1～2000 μ m) but at least one surface be immersed in crystallization and become in the synthesized gel rubber of zeolite type material, make zeolite type material on the substrate surface crystallization, repeat these steps of one or many after the taking-up again, obtain the mould material of zeolite type material direct crystallization on base material.Porous substrate is being immersed before synthesized gel rubber carries out crystallization, can be earlier at substrate surface in conjunction with last layer Ni, Co, Mo metal or its oxide compound (EP 0481658Al), and/or, perhaps base material is carried out sour pre-treatment (EP0481659A1) in conjunction with the oligopolymer (WO 93/19840) of last layer silicic acid.
The zeolite type material that loads in the above-mentioned patent on the base material all is the material that is used for membrane sepn, promptly has the material that maximum surface/body is compared, base material wherein all must be a porous material, zeolitic material wherein all is to be filled in the duct of porous substrate to form tight zone, should control the appearance of " pinprick " in order to avoid influence the effect of membrane sepn as far as possible.At present also not with zeolite type material load bibliographical information with preparation catalytic distillation structure and irregular shape catalyst on the specified shape base material, if the zeolite type material can be made catalytic distillation structure or irregular shape catalyst, bring revolutionary breakthrough and beneficial effect will for catalysis engineering field.
Though there are many scholars that active ingredient ZSM-5 molecular sieve is compound in asbestos (USP4511667, catalysis journal 11 (3) 204-209 (1990)), make matrix material on vermiculite (CN 1059673A), the silica gel (CN 1084100 A), but still have the problem of shaped catalyst, promptly do not solve the problem of catalyzer geometrical shape in the industrial application process.
The purpose of this invention is to provide a kind of new catalytic composite materials, the ZSM-5 molecular sieve directly is compound on metal or the ceramic base material, it can be used as excellent catalytic distillation structure, catalyzed reaction and product separation energy while continuous high-efficient ground in same tower is carried out, also can use to strengthen mass transfer, heat transfer and the reduction pressure drop of logistics as special-shaped catalyst, reduce the thickness of catalyst layer simultaneously, improve the utilization ratio of catalyzer.
Catalytic composite materials provided by the present invention directly is compound in ZSM-5 molecular sieve thin layer in advance equably, securely and designs as required, arbitrary shape, the arbitrarily metal of size or ceramic base material surface and the catalytic composite materials that forms.
ZSM-5 molecular sieve on the said matrix material can be various ZSM-5 molecular sieves included in the prior art, it can be the molecular sieve of pure silicon or sial, it also can be the molecular sieve that contains other heteroatomss such as boron, phosphorus, iron etc., its silica alumina ratio is 20～∞, and can carry out various modifications to enlarge its range of application to the molecular sieve on this matrix material.
The material of said metal base can be that pure metal comprises iron, nickel, copper, molybdenum, aluminium, magnesium, chromium, titanium, vanadium, manganese, zinc etc., also can be that the alloy that contains these metals comprises various stainless steels, various aluminium alloy, each Albatra metal-etc.; The crystalline phase of said ceramic base material can be an oxysalt, as silicate, titanate, zirconate etc., also can be oxide compound, nitride and carbide etc.Metal wherein or ceramic base material are dense materials, it also can be porous material, the design arbitrarily as required of its shape and big I, as be designed to dumped packings such as θ ring, rectangular saddle ring, cascade ring, Pall ring, regular filler such as waved plate, ripple silk net, and the shape and the size of special-shaped catalyst such as static mixer, cellular integral catalyzer, wheel shape.
The thickness of ZSM-5 molecular sieve thin layer is 5～500 microns in the said matrix material.Because the molecules of active components of this matrix material sieve layer can be very thin, matrix material will keep the geometrical shape and the size of metal base, can design the shape and the size of metal base according to the requirement of concrete application, that is to say that the Flow of Goods and Materials state can be determined by the design of metal base in the use.
The preparation method of said matrix material provided by the present invention is immersed in crystallization in the synthetic liquid that can synthesize the ZSM-5 zeolite molecular sieve with metal or ceramic base material, take out after washing, drying, perhaps repeat this submergence crystallization steps of one or many again, obtain catalytic composite materials of the present invention, it can carry out modification by ion-exchange or other method before use.
The said synthetic liquid that can synthesize the ZSM-5 zeolite molecular sieve can design its composition and prescription by prior art, but the amount of water is big when more synthetic than routine, wherein can contain silicon sources such as silicon sol or water glass, aluminium source such as sodium metaaluminate, aluminium salt or replace other heteroatoms of aluminium such as boron, phosphorus, iron etc., mineral alkali and/or organic bases, water and organic ammonium template.Wherein preferable molar ratio scope is SiO
2/ Al
2O
3=20～∞, Na
2O/SiO
2=0.03～0.4, R
+(organic ammonium)/SiO
2=0.05～0.5, H
2O/SiO
2=40～400.
Said organic ammonium template can be all the organic ammonium template that can synthesize the ZSM-5 molecular sieve, as tetraethylammonium bromide, 4-propyl bromide etc.
Condition when the condition of said crystallization is synthesized the ZSM-5 zeolite with routine is identical, and wherein crystallization temperature is 120～200 ℃, and crystallization time is 0.5～10 day.
In recombination process, will need the metal or the ceramic base material of composite molecular screen to be immersed in the synthetic liquid, but the buried time can change, as metal or ceramic base material and synthetic liquid are put into synthesis reactor simultaneously, also can be earlier with synthesize liquid at a certain temperature crystallization put into base material after for some time again, also can take out matrix material after compound at different crystallization times.
Catalytic composite materials provided by the present invention has following advantage as catalytic distillation structure and irregular shape catalyst:
I) its geometrical shape and big I are flexible and changeable as required, to reduce pressure drop, improve mass transfer and heat transfer efficiency, the catalytic distillation process is efficiently successfully carried out, and make product in time shift out reaction zone, improve the transformation efficiency and the selectivity of catalyzed reaction;
II) the ZSM-5 active ingredient is distributed in substrate surface equably, has improved the geometrical surface of catalyzer;
III) the active ingredient layer thickness is less and can regulate, and than custom catalysts higher utilization ratio is arranged;
IV) can carry out modulation and modification to ZSM-5 active ingredient layer and do not influence the intensity of active coating, make the range of application of ZSM-5 unrestricted.
Fig. 1,2,3,4 is respectively metal or the figure of the scanning electron microscope (SEM) before and after the ceramic base material surface recombination ZSM-5 molecular sieve among the embodiment 2,5,12,15.Wherein a represents the surface before the composite molecular screen, and b represents the surface after compound.
Fig. 5, Fig. 6 are respectively metal or the figure of the X-ray diffraction (XRD) before and after the ceramic base material surface recombination ZSM-5 molecular sieve among the embodiment 2,5.Wherein a represents the sample before the composite molecular screen, and b represents the sample after compound.
The following examples will the present invention is further illustrated.
The thing on the catalytic composite materials surface of preparing in the example does not detect by X-ray diffraction (XRD) mutually; The pattern on surface is observed by scanning electron microscope (SEM); The body phase SiO of molecular sieve layer
2/ Al
2O
3Be to measure by plasma emission spectroscopy method (ICP) from the powder molecular sieve that matrix material scrapes off; The thickness of molecular sieve layer is by the SEM undetermined on the matrix material cross sections.
Example 1～3
Measure three parts of 0.1N NaAlO respectively
2Each 50ml of (Beijing Chemical Plant) each 50ml and 0.1N NaOH (Jinzhou, Liaoning chemical reagent factory) puts into three beakers, taking by weighing three parts of each 5.0g of TPABr (Tokyo changes into Co., Ltd.) adds in the above-mentioned beaker, add deionized water 1 more respectively) 180ml, 2) 240ml, 3) stir behind the 320ml three parts of solution, measure silicon sol (25%SiO again
2, Wenzhou catalyst plant) three parts of each 20ml join respectively in above-mentioned three parts of solution, stir synthetic liquid.These synthetic liquid are poured into respectively in three synthesis reactors that stainless steel φ 3 * 3 * 0.1mm θ ring filler (Iron and Steel Research Geueral Inst filler factory provides) has been housed, take out two days later and wash in 180 ℃ of following crystallization, found that three samples all have uniform, firm ZSM-5 molecular sieve layer to be compound in the metallic surface, its thickness is respectively 1 after measured) 64um; 2) 42 μ m; 3) 21um, and along with water-content in the synthetic liquid increases and reduces.Wherein the SEM photo of second the compound ZSM-5 molecular sieve of sample front and back is seen Fig. 1, and XRD spectra is seen Fig. 5.
Example 4
The same procedure of pressing example 2 is synthetic, and recording molecular sieve layer thickness after the washing drying is 45 μ m; And then with this matrix material carry out the second time with the quadrat method crystallization after, its molecular sieve thickness is 93 μ m, this matrix material is carried out for the third time with after the quadrat method crystallization, its molecular sieve thickness is 138 μ m, this matrix material is carried out the 4th time with after the quadrat method crystallization, its molecular sieve thickness is 201 μ m, illustrates that molecular sieve thickness increases with the crystallization number of times.At last molecular sieve layer is scraped off and record its SiO
2/ Al
2O
3Be 54.1.
Example 5
The amount of pressing example 2 adds NaAlO
2, NaOH, TPABr and deionized water, different is to add silicon sol (25%SiO
2Wenzhou catalyst plant) amount is 32ml, and base material uses cordierite ceramic sheet (Chinese Academy of Sciences ecological center product) instead, and is synthetic under the condition identical with example 2, the result on this ceramic plate same on compound uniform, firm ZSM-5 molecular sieve layer, record the SiO of molecular sieve layer
2/ Al
2O
3Be 70.5.Its SEM photo is seen Fig. 2, and XRD figure is seen Fig. 6.
Example 6
It is synthetic to press example 2 methods, and unique difference is not add NaAlO
2, finding have uniform total silicon zeolite topped on stainless steel φ 3 * 3 * 0.1mm θ ring filler (Iron and Steel Research Geueral Inst filler factory provides) after eight days 180 ℃ of crystallization, its XRD figure and Fig. 5 are similar.
Example 7～10
Measure 0.1N NaAlO respectively
2Each 50ml and each 50ml of 0.1N NaOH put into four beakers, take by weighing 7) TPABr 2.5g, 8) TPABr 5.0g, 9) TPABr 10.0g, 10) TEABr (Beijing Chemical Plant) 5.0g puts into above-mentioned four beakers respectively, add respectively then each 160ml of deionized water stir solution.Measure silicon sol (25%SiO again
2) four parts of each 40ml join respectively in above-mentioned four solution, stir synthetic liquid.These synthetic liquid are poured into respectively in four synthesis reactors that φ 14 * 32mm cordierite honeycomb ceramic (Chinese Academy of Sciences ecological institute) has been housed, 150 ℃ of following crystallization find after five days four samples all equably, compound securely on the ZSM-5 molecular sieve layer.
Example 11～14
By the example 8 synthetic liquid of preparation that feeds intake, but base material adopts 11 respectively) pure iron, 12) pure nickel, 13) fine aluminium, 14) the Al-alloy metal sheet.To synthesize liquid earlier at 180 ℃ of crystallization 2hr, put into above-mentioned metal base then, continue crystallization two days later, find all compound even, firm ZSM-5 molecular sieve layer on four kinds of metallic substrate surface.Wherein sample 12) the SEM photo see Fig. 3.
Example 15～16
By the example 8 synthetic liquid of preparation that feeds intake, but ceramic base material adopts 15 respectively) pure aluminium sesquioxide ceramic plate (Dalian Chemical Physics Research Institute), 16) φ 14 * 32mm cordierite honeycomb ceramic.To synthesize liquid earlier at 180 ℃ of crystallization 2hr, put into above-mentioned ceramic base material then, continue crystallization two days later, find all compound even, firm ZSM-5 molecular sieve layer on two kinds of ceramic base material surfaces.Wherein sample 15) the SEM photo see Fig. 4.
Example 17～19
By the example 7 synthetic liquid of preparation that feeds intake, but the cordierite ceramic base material adopts 17 respectively) industrial Dg25 cascade ring filler, 18) industrial Dg 25 ceramic Intalox saddles (Pingxiang City petrochemical industry porcelain structured packing factory), 19) φ 3 * 3mm ceramic honey comb (Chinese Academy of Sciences's ecological center product).With finding two days later that with the same method crystallization of example 7 three kinds of difform ceramic base materials are all covered equably by the ZSM-5 molecular sieve layer.
Example 20
According to the method for example 19 20ml φ 3 * 3mm ceramic honey comb filler is carried out that its compound molecular sieve amount is 1.8569g after twice crystallization.This sample is carried out temperature-programmed calcination, and its heat-up rate is 1 ℃/min, difference constant temperature 1hr, 2hr, 6hr under 120 ℃, 300 ℃, 450 ℃ three ladder temperature, last naturally cooling.Sample after the roasting is put into 1M NH
4In the Cl solution, stir down in 90 ℃ and to carry out ion-exchange 2hr, again with deionized water wash to there not being Cl
-(AgNO
3Detect), at this moment ZSM-5 has finished NH
4 +Exchange.At last this matrix material is made a strength test, the matrix material that is about to this process ion-exchange is put into the glass distillation tower of φ 25.4 * 600mm, with benzene-tetracol phenixin is that system is returned entirely and heated up in a steamer, each 8hr that continues, repeated experiments is 20 times like this, then matrix material is taken out washing, dry, weighing, its molecular sieve reservation amount is 1.8489g, and its retention value is 99.6%.
Example 21～23
Adopt example 20 synthetic ZSM-5/ ceramic composites, through NH
4 +After the ion-exchange as catalyzer, on the fixed bed of φ 25.4mm, L400mm, carry out the reaction of propyl acetate+propyl carbinol butylacetate+propyl alcohol, its condition is: pure HZSM-5 amount is 6: 1 for propyl carbinol/propyl acetate (mol) in the 8.3327g raw material, temperature of reaction is 1175 ± 1 ℃, and mass space velocity is respectively 21) 1.59hr
-1, 22) and 2.39hr
-1, 23) and 7.96hr
-1, adopt HP5890 gas chromatograph analytic sample to form, the result is that transformation efficiency is respectively 16) 58.2%, 17) 49.2%, 18) 35.6%.
Claims (10)
1.ZSM-5 molecular sieve directly is compounded in the catalytic composite materials that can be used as catalytic distillation structure or irregular shape catalyst on metal or the ceramic base material, it is characterized in that this matrix material is made up of the pre-designed shape with dumped packing, structured packing, static mixer, special-shaped catalyst and integral catalyzer of ZSM-5 molecular sieve and this molecular sieve of load and the metal or the ceramic base material of size or shape similarly and size.
2. according to the catalytic composite materials of claim 1, it is characterized in that said ZSM-5 molecular sieve is the molecular sieve of sial or pure silicon, or contain the heteroatomic molecular sieve that comprises boron, phosphorus, iron, its SiO
2/ Al
2O
3Mol ratio is 20～∞.
3. according to the catalytic composite materials of claim 1, it is characterized in that ZSM-5 molecular sieve wherein can carry out modification by the method for prior art.
4. according to the catalytic composite materials of claim 1, the thickness that it is characterized in that the ZSM-5 molecular sieve layer is 5～500 microns.
5. according to the catalytic composite materials of claim 1, the material that it is characterized in that said metal base is the pure metal of chosen from Fe, nickel, copper, molybdenum, aluminium, magnesium, chromium, titanium, vanadium, manganese or zinc, or is selected from the metal alloy of stainless steel, aluminium alloy or copper alloy; The crystalline phase of its ceramic base material is the oxysalt that is selected from silicate, titanate or zirconate, or their oxide compound, nitride or carbide.
6. the preparation method of the said catalytic composite materials of claim 1 is characterized in that this method comprises said metal or ceramic base material are immersed in the H that can synthesize the ZSM-5 molecular sieve
2O/SiO
2Mol ratio is that hydrothermal crystallizing is at least once according to a conventional method in 40～400 the synthetic liquid.
7. according to the preparation method of claim 6, it is characterized in that other heteroatomss, mineral alkali or the organic bases, water and the organic ammonium template that contain silicon source, aluminium source in the said synthetic liquid that can synthesize the ZSM-5 molecular sieve and/or replace aluminium.
8. according to the preparation method of claim 7, it is characterized in that the molar ratio scope is SiO in the said synthetic liquid
2/ Al
2O
3=20～∞, Na
2O/SiO
2=0.03～0.4, R
+(organic formwork agent)/SiO
2=0.05～0.5, H
2O/SiO
2=40～400.
9. according to the preparation method of claim 6, the condition that it is characterized in that said crystallization is that temperature is 120～200 ℃, and the time is 0.5～10 day.
10. the described catalytic composite materials of claim 1 is as the application of catalytic distillation structure or special-shaped catalyst.
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| CN96109109A CN1058643C (en) | 1996-07-22 | 1996-07-22 | Catalytic ZSM-5/metal or ceramic compounded material and its preparation |
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Publications (2)
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|---|---|
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| CN1058643C true CN1058643C (en) | 2000-11-22 |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100563829C (en) * | 2008-02-03 | 2009-12-02 | 山东省科学院能源研究所 | Integral supported carbon molecular sieve catalyst and preparation method thereof is used |
| CN103449474B (en) * | 2012-06-01 | 2014-12-31 | 中国石油化工股份有限公司 | Phosphorus-containing ZSM-5 molecular sieve membrane and preparation method thereof |
| CN104525255A (en) * | 2014-12-23 | 2015-04-22 | 中国科学院过程工程研究所 | Preparation method for supporting ordered mesoporous molecular sieve SBA-15 on metal foam matrix |
| CN112517053A (en) * | 2020-12-30 | 2021-03-19 | 福州大学 | Preparation method of high-performance supported catalytic filler |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4443559A (en) * | 1981-09-30 | 1984-04-17 | Chemical Research & Licensing Company | Catalytic distillation structure |
| CN1059673A (en) * | 1991-05-21 | 1992-03-25 | 南京大学 | Composited HZSM-5 zeolite/vermiculite catalyst and uses thereof |
| EP0481658A1 (en) * | 1990-10-19 | 1992-04-22 | The British Petroleum Company P.L.C. | Deposition process |
| EP0481660A1 (en) * | 1990-10-19 | 1992-04-22 | The British Petroleum Company P.L.C. | Membranes |
| CN1084100A (en) * | 1992-09-09 | 1994-03-23 | 中国石油化工总公司石油化工科学研究院 | The preparation of ZSM-5 zeolite/silica-gel composite catalyst material |
-
1996
- 1996-07-22 CN CN96109109A patent/CN1058643C/en not_active Expired - Lifetime
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4443559A (en) * | 1981-09-30 | 1984-04-17 | Chemical Research & Licensing Company | Catalytic distillation structure |
| EP0481658A1 (en) * | 1990-10-19 | 1992-04-22 | The British Petroleum Company P.L.C. | Deposition process |
| EP0481660A1 (en) * | 1990-10-19 | 1992-04-22 | The British Petroleum Company P.L.C. | Membranes |
| CN1059673A (en) * | 1991-05-21 | 1992-03-25 | 南京大学 | Composited HZSM-5 zeolite/vermiculite catalyst and uses thereof |
| CN1084100A (en) * | 1992-09-09 | 1994-03-23 | 中国石油化工总公司石油化工科学研究院 | The preparation of ZSM-5 zeolite/silica-gel composite catalyst material |
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| Publication number | Publication date |
|---|---|
| CN1171294A (en) | 1998-01-28 |
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